EP1331985B1 - Verfahren zur herstellung einer emulsion, deren organische phase eine hohe viskosität hat - Google Patents

Verfahren zur herstellung einer emulsion, deren organische phase eine hohe viskosität hat Download PDF

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Publication number
EP1331985B1
EP1331985B1 EP01980622A EP01980622A EP1331985B1 EP 1331985 B1 EP1331985 B1 EP 1331985B1 EP 01980622 A EP01980622 A EP 01980622A EP 01980622 A EP01980622 A EP 01980622A EP 1331985 B1 EP1331985 B1 EP 1331985B1
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Prior art keywords
polymer
process according
aqueous phase
heat
organic phase
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French (fr)
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EP1331985A2 (de
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Hélène LANNIBOIS-DREAN
Mikel Morvan
Marie-Pierre Labeau
Christine Vidil
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Rhodia Chimie SAS
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Rhodia Chimie SAS
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/062—Oil-in-water emulsions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/06—Emulsions
    • A61K8/066—Multiple emulsions, e.g. water-in-oil-in-water
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/90—Block copolymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017—Mixtures of compounds
    • C09K23/018—Mixtures of two or more different organic oxygen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/18—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/22—Amides or hydrazides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/20—Chemical, physico-chemical or functional or structural properties of the composition as a whole
    • A61K2800/24—Thermal properties
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/54—Polymers characterized by specific structures/properties

Definitions

  • the subject of the present invention is a process for preparing an emulsion of which the organic phase has a high viscosity.
  • Difficulties are encountered in preparing emulsions having a relatively small droplets, and obtained from a continuous aqueous phase and an organic discontinuous phase whose viscosity is high, that is to say at least equal to 1 Pa.s, preferably at least 5 Pa.s. Indeed, the difference in viscosity between the continuous and discontinuous phases makes it necessary to implement very shearing and / or unproductive means. In addition, the results achieved are only partially satisfactory.
  • thermo-thickening polymer The preparation of oil-in-water emulsions using a thermo-thickening polymer is disclosed in WO-A-9700275 and WO-A-95 04774. Polymers thermo-thickeners are described in US-A-5,658,981.
  • the object of the present invention is to obtain a simple and effective method of preparation of an oil-in-water emulsion from a viscous organic phase, that is to say, on the one hand, requiring only conventional means, and on the other hand, to obtain a particle size for the emulsion, fine and regular.
  • the present invention is particularly suitable for obtaining multiple emulsions.
  • the subject of the present invention is a process for preparing an oil-in-water emulsion, the organic phase of which has a viscosity greater than or equal to 1 Pa.s in which an aqueous phase comprising at least one thermo-thickening polymer is used.
  • thermo-thickening polymer having a viscosity leap between 25 and 80 ° C such that the value of log 10 (viscosity at 80 ° C) / log 10 (viscosity at 25 ° C) is at least 1, preferably at least 2 the variation of the viscosity being reversible; the amount of thermo-thickening polymer being such that the viscosity of the aqueous phase is 0.2 to 5 times that of the organic phase at the emulsion preparation temperature; this being greater than or equal to the thickening temperature of the heat-thickening polymer.
  • the process according to the invention can be implemented for obtaining simple oil-in-water emulsions, but also for emulsions multiple for which the organic phase is in fact an inverse emulsion (thus water in oil).
  • the average size of the droplets of a single emulsion obtained according to the invention is more particularly between 0.1 and 50 ⁇ m, preferably between 0.1 and 5 ⁇ m.
  • the average size droplets dispersed in the external aqueous phase are between 5 and 100 ⁇ m, more particularly between 5 and 50 ⁇ m, advantageously between 5 and 15 ⁇ m.
  • the average sizes of the droplets are measured using a Horiba granulometer, and correspond to the volume median diameter (d 50 ) which represents the diameter of the particle equal to 50% of the cumulative distribution.
  • emulsion is used interchangeably to designate a simple direct emulsion (oil in water), an inverse emulsion (water in oil) or a multiple emulsion, unless the nature of the emulsion is indicated precisely.
  • aqueous phase for designate the aqueous phase of the inverse emulsion of the multiple emulsion.
  • aqueous phase will mean indifferently the aqueous phase of a simple emulsion direct, or the "external" aqueous phase of a multiple emulsion.
  • polymers refers to both homopolymers and copolymers.
  • the compound used as the organic phase is more particularly chosen from compounds whose solubility in water does not exceed 10% by weight at 25 ° C.
  • the organic phase has a viscosity of at least 1 Pa.s, preferably at least 5 Pa.s.
  • the process according to the invention is particularly suitable for the preparation of emulsions for wherein the organic phase has a viscosity of between 5 and 500 Pa.s.
  • the viscosity refers to the dynamic viscosity measured at 25 ° C. using a Brookfield viscometer according to the AFNOR NFT 76 102 standard of February 1972.
  • the organic phase is more particularly chosen from mineral oils; the alkyd resins (such as Coporob 3115 DE resins, sold by the company Novance); polyisocyanates; silicones of high molecular weight; these compounds being alone or in mixture.
  • polybutene oils examples include polybutene oils.
  • the polybutene oils obtained by polymerization of the C proportion of isobutene is high (Napvis, Hyvis ranges of BP).
  • polyisocyanates there may be mentioned in particular the compounds of the following formula: A (-NCObloc) p , where A represents an organic skeleton having n free valencies, p being between 2 and 7, NCObloc represents a masked isocyanate function or not.
  • the total number of carbons of said monomer is advantageously between 10 and 100.
  • skeleton A can be made from a heavy polyamine, including including anilines, for example having a carbon number of at least 6, more particularly at least 10, preferably at least 15. This amine is converted in a manner known per se by reaction with phosgene. It is note that the skeleton A can also be that of trimers and biurets.
  • the masking agents are chosen so that the emulsion is stable at its storage temperature.
  • Suitable polyisocyanates are more particularly chosen from oils and / or gums and / or resins containing (poly) isocyanates groups whose viscosity found in the ranges indicated before. We would not go beyond the invention using several compounds of this type, as well as their association with at least one solvent (or diluent) of said oil and / or gum and / or resin, as soon as the instant that the viscosity of the whole is in the indicated range.
  • silicones of high molecular weight mention may be made, for example, of oils and / or gums and / or polyorganosiloxane resins. We would not go beyond the scope of the present invention using mixtures of oil (s) and / or gum (s) and / or polyorganosiloxane resin (s), as soon as the mixtures present a viscosity in the ranges indicated above.
  • the invention is suitable for emulsifying mixtures of oil (s) and / or gum (s) and / or polyorganosiloxane resin (s), and optionally at least one solvent of said oil (s) and / or gum (s) and / or resin (s), and / or optionally at least one silane and / or at least one siliceous or non-siliceous filler, as long as the mixtures have viscosities in the mentioned area.
  • At least 80% of the radicals R of said oils representing a methyl group Preferably at least 80% of the radicals R of said oils representing a methyl group.
  • polyorganosiloxane resins that can be used, there may be mentioned those consisting of units of formulas: R Si O 3/2 (T-pattern) and / or Si O 2 (Q-pattern) associated with formulas reasons: R ' 3-a R a Si O 1/2 (M-pattern) and / or R 2 Si O (D-pattern) formulas in which a, R and R 'are as defined above.
  • oils, gums or resins contain reactive radicals R and / or polar, such as H, OH, vinyl, allyl, hexenyl, aminoalkyls in particular, these The latter do not generally represent more than 2% of the weight of the oil or gum and not more than 10% by weight of the resin.
  • Polydimethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxane oils as polydimethylsiloxanes, polyphenylmethylsiloxane and ⁇ , ⁇ -bis (hydroxy) polydimethylsiloxanes are well-known commercial products.
  • the viscous polymethylsiloxane resins DT containing from 1 to 2% by weight of Silanol functions are also commercially available products.
  • oils volatile cyclic organopolysiloxanes (octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, ...), the oils short polydimethylsiloxanes (viscosity less than 100 mPa.s.), hexamethyldisiloxane, ketones (methyl ethyl ketone, etc.) ethers (diethyl ether) %), esters (isopropyl myristate, ethyl acetate, ......), certain chlorinated solvents or chlorofluorinated (methylene chloride, chloroform ...), paraffins very branched (white oils based on isoalkanes and cycloalkanes ).
  • volatile cyclic organopolysiloxanes octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, Among the solvents of oils, gums or silicone resins,
  • Silanes and / or various mineral fillers can likewise be present in the silicone phase.
  • silanes can be, in particular, by-products of synthesis or agents for crosslinking said oils, gums or polyorganosiloxane resins. They are generally present in amounts of the order of 0 to 10 parts by weight, preferably of the order of 0 to 5 parts by weight per 100 parts by weight of oil (s) and / or gum (s) and / or polyorganosiloxane resin when it comes to by-products reaction.
  • oils, gums or resins hydroxylated When their function as a crosslinking agent for oils, gums or resins hydroxylated is sought, they are usually present in amounts of in the range of 0.5 to 30 parts by weight, preferably of the order of 2 to 8 parts by weight per 100 parts by weight of oil (s) and / or gum (s) and / or resin (s).
  • Said silanes may also be an additive for modulating the properties physicochemical, adhesion including silicone application compositions various products obtained from aqueous emulsions prepared by the process of the invention.
  • this category of silanes mention may be made of aminopropyltriethoxysilane, aminopropylmethyldiethoxysilane, glycidoxypropyltrimethoxysilane ... They are used in quantities of up to 200%, usually from the order of 2 to 100% by weight of oil (s) and / or gum (s) and / or resin (s).
  • Siliceous or non-siliceous reinforcing or semi-reinforcing fillers may also be present.
  • colloidal silicas Silica powders of combustion and precipitation, diatomaceous earth, quartz milled, natural calcium carbonate, hydrated alumina, magnesium hydroxide, carbon black, titanium dioxide, aluminum oxide, vermiculite, zinc, mica, talc, iron oxide, barium sulphate, slaked lime ...
  • the size of these charges is generally less than or equal to the average size of the droplets in which they are dispersed.
  • the average size of these fillers (d 50 ) is generally of the order of 0.001 to 50 ⁇ m, preferably of the order of 0.001 to 10 ⁇ m.
  • Charges are generally present in quantities that can go up to 300%, preferably of the order of 3 to 100% by weight of oil (s) and / or gum (s) and / or resin (s).
  • the organic phase may optionally comprise at least one active ingredient hydrophobic.
  • organic phase itself may constitute the active ingredient hydrophobic as soon as the organic phase has a dynamic viscosity in the range indicated above.
  • the active ingredient present in liquid form or not, soluble in the organic phase or solubilized in an organic solvent miscible with said organic phase, or in the form a solid dispersed in said phase.
  • the active ingredients are such that their solubility in water does not exceed 10% by weight at 25 ° C.
  • the active materials preferably have a melting temperature less than or equal to 100 ° C, more particularly less than or equal to 80 ° C.
  • silicone oils belonging for example to the family of dimethicones; the lipophilic vitamins like vitamin A.
  • phytosanitary active ingredients can be be selected from the family of ⁇ -cyano-phenoxybenzyl carboxylates or ⁇ -cyano-halophenoxy carboxylates, the family of N-methylcarbonates comprising aromatic substituents, active ingredients such as Aldrin, Azinphos-methyl, Benfluralin, Bifenthrin, Chlorphoxim, Chlorpyrifos, Fluchloralin, Fluroxypyr, Dichlorvos, Malathion, Molinate, Parathion, Permethrin, Profenofos, Propiconazole, Prothiofos, Pyrifenox, Butachlor, Metolachlor, Chlorimephos, Diazinon, Fluazifop-P-butyl, Heptopargil, Mecarbam, Propargite, Prosulfocarb, Bromophos-ethyl, Carbophenothion, Cyhalothrin.
  • active ingredients such as Aldrin, Azinphos-methyl,
  • the active ingredient is usually an oil, a derivative of an oil or an ester of fatty acid or a fatty acid salt.
  • the active ingredient can also be chosen from organic solvents or mixtures of such solvents not or not very miscible in water, such as those used for cleaning or stripping, such as oil cuts aromatic compounds, terpene compounds such as D- or L-limonenes, and solvents like Solvesso®.
  • Esters are also suitable as solvents aliphatics, such as the methyl esters of a mixture of acetic and succinic acids and glutaric (acid mixture by-product of nylon synthesis), oils like Vaseline oil, and chlorinated solvents.
  • the organic phase comprises one or more active ingredients different hydrophobic properties of the organic phase
  • their content represents more particularly 1 to 50% by weight of said organic phase.
  • the organic phase comprises a dispersed internal aqueous phase. More particularly, the organic phase is a inverse emulsion.
  • the viscosity of the inverse emulsion that is to say of the organic phase including the internal aqueous phase, also has a high viscosity.
  • the viscosity of the inverse emulsion is at least 1 Pa.s, more particularly from at least 5 Pa.s and preferably between 5 and 500 Pa.s.
  • Viscosities mentioned above are dynamic viscosities measured at Brookfield at 25 ° C, according to the NFT 76 102 standard of February 1972.
  • the organic phase of the inverse emulsion is preferably from same nature as that of a simple emulsion. We can therefore refer in every respect to the list given above.
  • the internal aqueous phase, if present, and / or the external aqueous phase of the emulsion may comprise at least one hydrophilic active material.
  • the hydrophilic active material is in the internal aqueous phase of the emulsion, when it is present.
  • hydrophobic and hydrophilic active substances are determined according to their compatibility with each other.
  • active ingredient hydrophilic is chosen so as not to interfere with the organic phase.
  • the hydrophilic active material may be in a form soluble in the aqueous phase ; in a solubilized form in a water-miscible solvent such as methanol, ethanol, propylene glycol, glycerol, for example; or under the form of a solid dispersion in said phase.
  • active materials which can be used in the field of cosmetics, substances that have a cosmetic effect, an effect therapy or any other substance that can be used for the treatment of skin and hair.
  • conditioning agents of the skin and hair such as polymers comprising ammonium quaternaries that may possibly be involved in heterocycles (quaternium compounds, polyquaternium, etc.), humectants; of the fixing agents (styling) which are more particularly chosen from polymers (Homo-, co- or ter-polymers, for example acrylamide, acrylamide / sodium acrylate, polystyrene sulfonate, etc.), cationic polymers, polyvinylpyrrolidone, acetate polyvinyl, etc.
  • polymers comprising ammonium quaternaries that may possibly be involved in heterocycles (quaternium compounds, polyquaternium, etc.), humectants; of the fixing agents (styling) which are more particularly chosen from polymers (Homo-, co- or ter-polymers, for example acrylamide, acrylamide / sodium acrylate, polystyrene sulfonate, etc.), cationic
  • coloring agents useful in deodorants and which are more particularly aluminum salts, zirconium; antibacterial agents; anti-inflammatory agents, agents anesthetics, sunscreens, etc.
  • ⁇ - and ⁇ -hydroxyacids such as citric acid, lactic acid, glycolic, salicylic; the dicarboxylic acids preferably unsaturated and comprising 9 to 16 carbon atoms such as azelaic acid; vitamin C and its derivatives, especially glycosylated and phosphated derivatives; biocides in particular cationic compounds (in particular Glokill PQ, Rhodaquat RP50, marketed by Rhodia Chemistry).
  • the divalent salts of calcium (phosphates, chlorides, etc.) used as crosslinking agent texturizing polymers such as alginates, carrageenans; baking soda sodium, among others.
  • hydrophilic pesticides or hydrophilic nutrients promoting growth and the development of plants.
  • the present invention can be implemented for hydrophilic active materials that can be used in particular during cementation operations, Completion, drilling and well stimulation (eg fracturing).
  • active ingredients which can be used in this field, mention may be made of catalysts for crosslinking cementitious compositions, such as, for example, lithium, like chloride, acetate.
  • catalysts for crosslinking cementitious compositions such as, for example, lithium, like chloride, acetate.
  • silicone field mention may for example be made of calcium salts, potash used as a crosslinking agent.
  • chloride calcium In the field of papermaking, mention may in particular be made of chloride calcium, hydrochloric acid.
  • the amount of hydrophilic active material is more particularly between 0.1 and 50% by weight relative to the aqueous phase (whether this is internal and / or external), preferably between 0.1 and 20% by weight relative to the phase aqueous (internal and / or external).
  • the weight ratio internal aqueous phase / organic phase is more particularly between 10/90 and 90/10. Preferably, this weight ratio is between 30/70 and 80/20.
  • the inverse emulsion further comprises at least one nonionic surfactant and / or at least one amphiphilic block polymer, and / or at least one cationic surfactant.
  • the inverse emulsion comprises at least one surfactant nonionic or at least one amphiphilic block polymer, or a mixture of them.
  • Bancroft rule can be applied to the nonionic surfactant and the amphiphilic block polymer used ( 2nd World Emulsion Congress, 1997, Bordeaux, France).
  • the fraction soluble in the continuous phase is greater than the fraction soluble in the dispersed phase.
  • nonionic surfactant is chosen from the compounds having a HLB (hydrophilic / lipophilic balance) value of less than or equal to 8.
  • Alkoxylated fatty alcohols generally comprise from 6 to 22 carbon atoms. carbon, the alkoxylated units being excluded from these numbers.
  • the alkoxylated triglycerides may be triglycerides of vegetable origin or animal.
  • the optionally alkoxylated sorbitan esters are esters of sorbitol cyclized fatty acid comprising from 10 to 20 carbon atoms such as the acid lauric acid, stearic acid or oleic acid.
  • Alkoxylated fatty amines generally have from 10 to 22 carbon atoms, the alkoxylated units being excluded from these numbers.
  • Alkoxylated alkylphenols generally have one or two linear alkyl groups or branched, having 4 to 12 carbon atoms. By way of example, mention may be made in particular octyl, nonyl or dodecyl groups.
  • amphiphilic block polymer it comprises at least two blocks.
  • amphiphilic polymers verifying the Bancroft rule and both conditions previously stated, more particularly include at least one hydrophobic block and at least one neutral, anionic or cationic hydrophilic block.
  • amphiphilic polymer comprises at least three blocks, and more especially three blocks
  • the polymer is preferably linear:
  • the blocks hydrophobes are more particularly at the ends.
  • the latter are of preferably in the form of graft polymers or combs.
  • polymer amphiphilic block will be used interchangeably for linear block polymers and graft polymers or combs.
  • Said amphiphilic polymers can advantageously be obtained by so-called living or controlled radical polymerization.
  • living or controlled polymerization processes it is particularly possible to refer to applications WO 98/58974 (xanthate), WO 97/01478 (dithioesters), WO 99/03894 (nitroxides); WO 99/31144 (dithiocarbamates).
  • Amphiphilic polymers can also be obtained by polymerization cationic, anionic.
  • They can likewise be prepared by involving polymerizations by ring opening (in particular anionic or cationic), or by chemical modification of the polymer.
  • Grafted polymers or combs can still be obtained by methods so-called direct grafting and copolymerization.
  • Direct grafting consists in polymerizing the monomer (s) selected by radical, in the presence of the polymer selected to form the skeleton of the product final. If the monomer / skeletal couple and the operating conditions are judiciously chosen, then there may be transfer reaction between the macroradical in growth and the skeleton. This reaction generates a radical on the skeleton and it is up to from this radical that grows the graft.
  • the primary radical derived from the initiator can also contribute to transfer reactions.
  • the copolymerization implements in a first time grafting at the end of the future segment during, of a polymerizable function by radical way. This grafting can be carried out by usual methods of chemistry organic. Then, in a second step, the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
  • Preferred monomers are esters of acrylic acid with linear or branched C 1 -C 4 alcohols such as methyl acrylate, ethyl acrylate, propyl butyl acrylate, vinyl esters such as vinyl acetate , styrene, ⁇ -methylstyrene.
  • nonionic hydrophilic monomers from which the Amphiphilic block polymers can be obtained it can be mentioned, without intention to limit itself, ethylene oxide, the amides of mono- or poly-carboxylic acids, linear, branched, cyclic or aromatic, comprising at least one ethylenic unsaturation or derivatives, such as (meth) acrylamide, N-methylol (meth) acrylamide; hydrophilic esters derived from (meth) acrylic acid as for example 2-hydroxyethyl (meth) acrylate; the vinyl esters to obtain polyvinyl alcohol blocks after hydrolysis, such as vinyl acetate, Versatate® vinyl propionate, alone, in combination, as well as macromonomers derived from such monomers.
  • macromonomer means a macromolecule carrying one or more functions polymerizable.
  • hydrophilic monomers are acrylamide and methacrylamide, alone or in admixture, or in the form of macromonomers.
  • hydrophilic anionic monomers from which the block amphiphilic polymers can be obtained it may be mentioned, for example monomers comprising at least one carboxylic, sulphonic or sulfuric function, phosphonic, phosphoric, sulfosuccinic, or the corresponding salts.
  • the functions of the anionic block or blocks of the polymer are in a form at least partially ionized (dissociated). In particular, at least 10% in mole functions of the block or blocks are in ionized form.
  • the determination of this value does not pose a problem to those skilled in the art; it is notably a function of pKa ionizable functions of the polymer units and the number of these functions (ie number of moles of monomer carrying ionizable functions used during the preparation of the polymer).
  • monomers precursors of those just mentioned have patterns which, once incorporated into the polymer chain, can be transformed, in particular by a chemical treatment such as hydrolysis, to restore the aforementioned anionic species.
  • the monomers totally or partially esterified of the aforementioned monomers may be work to be subsequently hydrolyzed totally or in part.
  • Said monomers may have a counter-ion chosen from halides such as chlorine, sulphates, hydrosulphates, alkyl sulphates (eg example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • halides such as chlorine, sulphates, hydrosulphates, alkyl sulphates (eg example comprising 1 to 6 carbon atoms), phosphates, citrates, formates, acetates.
  • the amphiphilic block polymers have a molar mass by weight less than or equal to 100000 g / mol, more particularly between 1000 and 50000 g / mol, preferably between 1000 and 20000 g / mol. It is stated that the masses molar weights given above are theoretical molar masses, evaluated according to the respective amounts of the monomers introduced during the preparation said polymers.
  • a non-block type amphiphilic polymer is used. ionic.
  • amphiphilic block polymer suitable for use of the invention, mention may be made of polyhydroxystearate-polyethylene triblock polymers glycol - polyhydroxystearate (ICI's Arlacel products are one of for example), polydimethylsiloxane block polymers polyether polyalkyl graft (like the Tegopren brand products marketed by Goldschmidt).
  • the inverse emulsion comprises at least one cationic surfactant.
  • the cationic surfactant does not verify not the Bancroft rule previously stated. Indeed, the cationic surfactant is soluble in the dispersed phase and not in the continuous phase of the inverse emulsion.
  • Suitable cationic surfactants it is especially possible to use the aliphatic or aromatic fatty amines, aliphatic fatty amides, derivatives thereof quaternary ammonium (Rhodaquat RP50 from Rhodia Chimie).
  • the total content of nonionic surfactant, in amphiphilic block polymer and / or cationic surfactant represents more in particular from 0.1 to 10% by weight, preferably from 2 to 10% by weight per relative to the internal aqueous phase.
  • the phase aqueous solution may comprise at least one additive selected from salts such as alkali metal or alkaline earth metal halides (such as sodium chloride, calcium chloride), or sulphates of alkali or alkaline earth metals (such as calcium sulphate), or mixtures thereof.
  • the internal aqueous phase can also include, as an additive, at least one sugar, such as glucose for example, or at least one polysaccharide, such as in particular dextran, or mixtures thereof.
  • the salt concentration in the internal aqueous phase when the latter is present, is more particularly between 0.05 and 1 mol / l, preferably 0.1 to 0.4 mol / l.
  • the concentration of sugar and / or polysaccharide is such that the pressure osmotic of the internal aqueous phase comprising said sugar and / or polysaccharide, corresponds to the osmotic pressure of an internal aqueous phase comprising 0.05 to 1 mol / l of salt.
  • the aqueous phase of the emulsion comprises at least one thermo-thickening polymer.
  • Thermo-thickening polymers have the particularity of giving aqueous solutions whose viscosity increases when the temperature exceeds thickening temperature of the thermo-thickening polymer; temperature beyond which viscosity of the medium in which is present said polymer increases.
  • these polymers are soluble in water at temperature ambient, and beyond the thickening temperature, some of the polymer becomes hydrophobic (thermosensitive part): the polymer thus forms a network microscopic scale, which translates into a macroscopic increase in viscosity.
  • thermo-thickening polymers used in the process according to the invention are chosen from those having a leap in viscosity between 25 and 80 ° C., such as the value of the log 10 ratio (viscosity at 80 ° C.). log 10 (viscosity at 25 ° C) is at least 1.
  • the polymer thermo-thickener has a leap in viscosity of at least one decade, preferably at least two decades.
  • thermo-thickening polymers are chosen from such that the variation of viscosity is reversible. In other words, the viscosity decreases when the temperature decreases.
  • thermo-thickening polymers that may be used, mention may be made of hydrophobic modified polysaccharides such as carboxymethyl celluloses, methyl celluloses, hydroxyethyl celluloses, hydroxypropyl celluloses.
  • Synthetic polymers such as polymers based on N-isopropyl are also suitable acrylamide, polymers based on N, N-dimethyl aminoethyl methacrylate.
  • the polymers thermo-thickeners used have a comb structure consisting of a Polymeric backbone segment on which at least two segments are grafted polymeric side elements, identical or not, for which either the polymeric backbone or the polymeric side segments have a lower critical temperature of solubility, LCST, between 25 and 80 ° C.
  • segments cover as well a sequence linear than branched.
  • polymeric backbone segment which has an LCST of between 25 and 80 ° C.
  • LCST between 25 and 80 ° C.
  • the segment that does not have the required LCST namely between 25 and 80 ° C, is water soluble at least in this area of temperatures, preferably between 10 and 100 ° C.
  • polymeric segment having no temperature LCST critic it is more preferably an ethylene-type polymer water-soluble.
  • water-soluble polymers may be derived from the polymerization of water-soluble ethylenic monomers.
  • These monomers may in particular be vinyl type, acrylic, styrenic, diene or vinyl ester type.
  • vinyl monomers By way of example of vinyl monomers, mention may be made of vinyl sulphonic acid, methallyl sulfonic acid or their salts.
  • acrylic monomers mention may be made of (meth) acrylic acid, diacids such as fumaric acid, itaconic acid, or their salts, anhydride maleic, acrylamide and its derivatives such as acrylamido methyl propane sulfonic acid or their salts.
  • styrenic monomers mention may be made of styrene sulphonic acid, vinyl benzoic acid or their salts.
  • hydrophobic monomers whose motifs, once incorporated into the polymer chain, can be converted, in particular by a chemical treatment such as than hydrolysis, in water-soluble patterns.
  • This is for example (meth) acrylate methyl, terbutyl (meth) acrylate, glycidyl (meth) acrylate and vinyl.
  • any organosoluble monomers may also be used and incorporated in the polymer chain in the form of hydrophobic units.
  • the different monomers are selected so that the corresponding polymeric segment has a solubility in aqueous medium compliant to the invention. This adjustment of relative amounts of corresponding monomers is within the skill of those skilled in the art.
  • Monomers such as acids, are especially preferred according to the invention.
  • acrylic or methacrylic acid, acrylamides and their derivatives, fumaric acids and maleic and sulfonated monomers such as 2-acrylamide-methyl-propane sulfonic acid and its alkali salts and vinylsulfonate.
  • this type of polymeric segment has a weight molecular weight at least greater than 1000 g / mol, and preferably at least greater than 20000 g / mol (measured by aqueous GPC, standard: POE).
  • these polymeric segments are derived from the polymerization of acrylic acid and / or 2-acrylamide-methyl-propane acid sulfonic acid.
  • polymeric segments with an LCST included between 25 and 80 ° C they are derived from polyoxyalkylene polymers.
  • the one or more oxyalkylene units present in the polyoxyalkylene polymer have at most 6 carbon atoms.
  • the segments presenting an LCST consist of of oxyethylene (OE) units and / or oxypropylene (OP) units.
  • the patterns OE and OP can be arranged in the heat-sensitive segment polymeric in statistical, block or sequenced form.
  • the heat-sensitive segment polymeric may for example have a starry structure. It is possible to adjust the critical temperature of solubility through especially the length and the composition of these polymeric segments.
  • the segments having a critical temperature according to the invention consist of at least 5 units oxyalkylene.
  • a macromonomer designates a macromolecule carrying one or more polymerizable ethylenic functions radical.
  • Grafting of polymeric side segments on a polymeric segment skeleton can be performed according to conventional techniques and familiar to the man from art (European Polymer Journal 4, 343 (1968) for example).
  • Direct grafting consists in polymerizing the monomer (s) selected by radical, in the presence of the polymer selected to form the skeleton of the product final. If the monomer / skeletal couple and the operating conditions are judiciously chosen, then there may be transfer reaction between the macroradical in growth and the skeleton. This reaction generates a radical on the skeleton and it is up to from this radical that grows the graft.
  • the primary radical derived from the initiator can also contribute to transfer reactions.
  • the copolymerization implements in a first time the grafting at the end of the thermosensitive segment of a polymerizable function per lane radical.
  • This grafting can be carried out by usual methods of chemistry organic.
  • the macromonomer thus obtained is polymerized with the monomer chosen to form the skeleton and a so-called "comb" polymer is obtained.
  • the polymer comprises 0.1% to 50% by mol and preferably 0.1 to 5.0 mol% of polymeric segments having an LCST of between 25 and 80 ° C.
  • the heat-thickening polymer content in the aqueous phase is such that the viscosity of the aqueous phase is 0.2 to 5 times that of the organic phase, preferably from 0.5 to 2 times that of the organic phase at the preparation temperature emulsion; this being greater than or equal to the thickening temperature of the thermo-thickening polymer.
  • thermo-thickening polymer content is more particularly between 0.5 and 5% by weight relative to the aqueous phase.
  • thermo-thickening polymer content is between 1 and 3% by weight per compared to the aqueous phase.
  • nonionic surfactants preference is given to polyalkoxylated nonionic surfactants.
  • the latter verifies the Bancroft rule and its two previously stated conditions, and includes at least two blocks, one of them being hydrophilic, the other hydrophobic; at least one blocks comprising polyalkoxylated units, more particularly polyethoxylated and / or polypropoxylated.
  • said polymers are obtained by involving ring-opening polymerizations, in particular anionic polymerizations.
  • nonionic polyalkoxylated amphiphilic polymers are chosen from polymers whose molar mass by weight is less than or equal to at 100000 g / mol (measured by GPC, polyethylene glycol standard), preferably included between 1000 and 50000 g / mol, preferably between 1000 and 20000 g / mol.
  • polymers of this type include, among others, triblock polymers polyethylene glycol / polypropylene glycol / polyethylene glycol. Of such polymers are well known and are especially marketed under the brand names Pluronic (marketed by BASF), Arlatone (marketed by ICI).
  • the nonionic amphiphilic polymer is a amphiphilic block polymer obtained by polymerization of at least one monomer nonionic hydrophilic material and at least one hydrophobic monomer, the proportion and the nature of said monomers being such that the resulting polymer satisfies the conditions previously stated (Bancroft rule - two conditions).
  • amphiphilic polymers furthermore comprise at least one hydrophobic block and at least one neutral hydrophilic block (nonionic).
  • the polymer comprises at least three blocks, and more particularly three blocks
  • the polymer is advantageously linear.
  • the hydrophilic blocks find more particularly at the ends.
  • the latter are of preferably in the form of graft polymers or combs.
  • hydrophilic nonionic monomers monomers nonionic hydrophobes, as well as the various methods of preparation cited in the context of the description of amphiphilic block polymers, can be repeated in the case of polymers according to this variant.
  • the preferred hydrophilic monomers are acrylamide and methacrylamide, alone or as a mixture, or in the form of macromonomers; the preferred monomers are esters of acrylic acid with linear or branched C 1 -C 4 alcohols such as methyl acrylate, ethyl acrylate, propyl butyl acrylate, vinyl esters such as vinyl acetate , styrene, ⁇ -methylstyrene.
  • Nonionic, anionic hydrophilic monomers, monomers as well as the modes of synthesis mentioned in the context of the description of the amphiphilic polymers used in the composition of emulsions for which the continuous phase is an oil phase, can be used to obtain polymers according to this variant. We can therefore refer to it.
  • the organic phase may be advantageous to add in the aqueous phase at least one additive selected from salts such as alkali metal halides, or alkaline earth halides (such as sodium chloride, calcium chloride), at least one alkali metal sulphate or alkaline earth (like calcium sulphate), at least one sugar (glucose per example), or at least one polysaccharide (especially dextran) or their mixtures.
  • salts such as alkali metal halides, or alkaline earth halides (such as sodium chloride, calcium chloride), at least one alkali metal sulphate or alkaline earth (like calcium sulphate), at least one sugar (glucose per example), or at least one polysaccharide (especially dextran) or their mixtures.
  • the emulsion according to the invention may be desirable to adjust the pH of the external aqueous phase by addition of base (soda, potassium hydroxide) or of (hydrochloric) acid.
  • the aqueous phase of the emulsion may comprise at least one thickening polymer.
  • This polymer has for effect of avoiding creaming and / or sedimentation of the final emulsion.
  • thickening polymers extracted from and optionally modified such as carrageenans, alginates, carboxymethyl celluloses, methylcelluloses, hydroxypropyl celluloses, hydroxyethyl celluloses.
  • thickening polymers of the type of polysaccharides of animal, plant or bacterial origin for example non-limiting example, xanthan gum, guar and derivatives (such as hydroxypropyl guar example), polydextroses, or combinations thereof.
  • the thickening polymer content is more particularly between 0.1 and 2% by weight relative to the aqueous phase, preferably between 0.1 and 0.5% by weight relative to the aqueous phase. Note that in this range concentration, the thickening polymer is soluble in the aqueous phase.
  • the weight ratio organic phase / aqueous phase, or the weight ratio of the whole internal aqueous phase and organic phase / aqueous phase is usually between 10/90 and 90/10, preferably between 30/70 and 80/20.
  • the preparation temperature of the emulsion is preferably greater than or equal to the melting temperature of the organic phase.
  • the equipment used for the agitation is all classical fact in the field.
  • agitation is rather slow, of the order of 300 to 700 revolutions / minute.
  • the process consists of first preparing the inverse emulsion and then mixing this last with the aqueous phase.
  • a first mixture comprising the compound constituting the internal organic phase and optionally the hydrophobic active material.
  • a second mixture comprising water, the surfactant and / or the nonionic and / or anionic amphiphilic polymer, the polymer thermo-thickening, optionally the active ingredient and / or the additive (salt, sugar and / or polysaccharide) and / or the thickening polymer.
  • the aqueous phase does not comprise any additive or of thickening polymer.
  • the preparation of the aqueous phase preferably consists of mixing all first the water and the active ingredient if it is used, then the surfactant and / or the polymer amphiphilic, with stirring. Then the thermo-thickening polymer is added,
  • This operation generally takes place at a temperature between 25 and 80 ° C, preferably between 40 and 70 ° C. It is not necessary that the temperature during the mixture of the various compounds of the aqueous phase is greater than or equal to thickening temperature of the heat-thickening polymer.
  • the emulsion is then obtained by adding the organic phase to the phase aqueous, with stirring. It is clarified again that according to a characteristic of the invention, this operation takes place at a temperature greater than or equal to temperature of thickening of the thermo-thickening polymer, so as to limit the difference in viscosity between the two phases of the emulsion.
  • this operation is carried out at a temperature of at least 25 ° C, more preferably between 25 and 80 ° C, preferably between 40 and 70 ° C.
  • the duration of the agitation can be determined without difficulty by those skilled in the art and depends on the type of equipment used. It is preferably sufficient for obtain an average droplet size (dso) within the indicated ranges before.
  • an example of preparation consists of preparing a first mixture constituting the internal aqueous phase, comprising water, optionally the hydrophilic active material, the cationic surfactant if present, and optionally the additive (salt, sugar and / or polysaccharide).
  • a second mixture is also prepared, comprising the compound constituting the internal organic phase, optionally the hydrophobic active material and the surfactant and / or the polymer amphiphile with nonionic blocks, if present.
  • the first mixture is then added to the second, with stirring.
  • the preparation of the inverse emulsion is generally carried out at a temperature greater than the melting temperature of the compound constituting the organic phase internal. More particularly, the preparation temperature of the inverse emulsion is between 20 and 80 ° C. Advantageously, the preparation temperature of the inverse emulsion is close to the preparation temperature of the multiple emulsion.
  • the duration of the agitation can be determined without difficulty by those skilled in the art and depends on the type of equipment used. It is preferably sufficient to obtain an average size of droplets (d 50 ) included in the ranges indicated above.
  • the external aqueous phase of the emulsion is then prepared.
  • This can include be carried out by mixing the surfactant and / or the nonionic amphiphilic polymer and / or anionic, the thermo-thickening polymer, optionally the active ingredient and / or the additive and / or the thickening polymer and the water.
  • the thermo-thickening polymer is added, and where appropriate, the thickening polymer.
  • the thickening polymer if it is used, is added once the multiple emulsion obtained. In this case, it is used in the form of a solution aqueous.
  • the water content is such that the concentration ranges of the emulsion multiple are verified.
  • This operation generally takes place at a temperature between 25 and 80 ° C, preferably between 40 and 70 ° C. It is not necessary that the temperature during the mixture of the various compounds of the external aqueous phase is greater than or equal to the thickening temperature of the heat-thickening polymer.
  • the next step is the preparation of the multiple emulsion itself adding the inverse emulsion to the aqueous phase which have been prepared previously.
  • This operation takes place at a temperature greater than or equal to the temperature thickening of the thermo-thickening polymer.
  • This operation therefore preferably takes place at a temperature of at least 25 ° C, more particularly between 25 and 80 ° C, preferably between 40 and 70 ° C.
  • the whole can be allowed to cool until a temperature below the thickening temperature of the polymer heat-induced.
  • the stirring conditions are preferably of the same type as those during the preparation of the inverse emulsion.
  • the emulsion according to the invention can be used as a constituent element in formulations that can be used in many fields, such as cosmetics, food, the field of phytosanitary active ingredients, that the exploitation or the construction of oil or gas wells, silicones, or in the field of papermaking, among others.
  • the macromonomer is synthesized en masse, without catalyst, in the way next :
  • Antarox E400 polymer triblock OE / OP / OE, marketed by Rhodia Chimie, 200 g
  • maleic anhydride (6.74 g).
  • the temperature is then raised to 60 ° C. (in approximately 1 hour), with stirring and nitrogen sweep, then at 140 ° C (in about 7 hours) and is maintained at this temperature for 18 hours.
  • the macromonomer obtained is then solubilized in water and neutralized in adding 5M sodium hydroxide.
  • thermo-thickening polymer is synthesized by a radical route in solution aqueous using acrylic acid and the macromonomer obtained above.
  • the polymerization is carried out at about 45 ° C.
  • the red-ox couple used is ammonium persulfate (oxidant) and the acid ascorbic (reducer).
  • the mass concentration of reactants is around 16%.
  • the reactor is then cooled.
  • This GPC is calibrated with POE standards; the molar masses obtained are therefore relative values.
  • the average molar mass is 310000 g / mol.
  • thermo-thickening polymer The viscosity of aqueous solutions containing the thermo-thickening polymer is measured as a function of temperature.
  • the measurement conditions are as follows:
  • the viscosity jump is measured in the imposed stress flow mode by conducting a temperature sweep between 20 ° C and 80 ° C.
  • the configuration used is the 4cm / 1degree cone-plane geometry.
  • the constraint introduced in the program is chosen (in manual mode) so that the gradient at 25 ° C is 10 s -1 .
  • the mixture is homogenized by stirring with a paddle frame at 250 rpm for 10 minutes. organic phase being placed in a water bath thermostated at 70 ° C.
  • the aqueous phase is then introduced dropwise under the same conditions stirring.
  • the amount of aqueous phase is such that the weight ratio aqueous phase / phase organic is 30/70.
  • the aqueous phase comprises 5.2 g of lactic acid (0.1M), 26.2 g of sodium (0.1M) and 0.18 g Phenonip (biocide, marketed by NIPA Laboratories).
  • the emulsion is refined by stirring at the frame for 10 minutes at 400 rpm and 15 minutes at 600 rpm.
  • the external aqueous phase is prepared as follows:
  • the initial pH is adjusted by adding sodium hydroxide (2M) to reach a pH 6-7 (measured at 23 ° C)
  • the resulting external aqueous phase is introduced into a water bath at 50 ° C. with stirring at the TT blade at 250 rpm until a homogeneous phase is obtained.
  • Phenonip 0.5 g Phenonip is then added.
  • the weight ratio internal aqueous phase / organic phase 1 external aqueous phase 16/35/49.
  • the average size of the droplets is between 5 and 10 ⁇ m (Horiba).

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Claims (24)

  1. Verfahren zur Herstellung einer Öl-in-Wasser-Emulsion, deren organische Phase eine Viskosität kleiner gleich 1 Pa.s aufweist, bei dem man eine wäßrige Phase verwendet, die mindestens ein thermoverdickendes Polymer enthält, welches einen derartigen Viskositätssprung zwischen 25 und 80°C aufweist, daß der Wert des Verhältnisses log10 (Viskosität bei 80°C)/log10 (Viskosität bei 25°C) mindestens gleich 1 und vorzugsweise mindestens gleich 2 ist, wobei die Viskositätsänderung reversibel ist; wobei die Menge an thermoverdickendem Polymer so groß ist, daß die Viskosität der wäßrigen Phase sich auf das 0,2- bis 5fache der Viskosität der organischen Phase bei der Herstellungstemperatur der Emulsion beläuft, wobei diese Temperatur größer gleich der Verdickungstemperatur des thermoverdickenden Polymers ist.
  2. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer mit Kammstruktur verwendet, das aus einer Polymerhauptkette besteht, auf die mindestens zwei gleiche oder verschiedene polymere Seitensegmente aufgepfropft sind, und bei dem entweder die Polymerhauptkette oder die Seitensegmente eine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweisen.
  3. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die Polymerhauptkette des Polymers eine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweist.
  4. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die Seitensegmente des Polymers eine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweisen.
  5. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein Polymer verwendet, das mehrere Polymere umfaßt, die so miteinander arrangiert sind, daß sie eine vernetzte Struktur bilden, in welcher die polymeren Segmente, die die untere kritische Lösungstemperatur aufweisen, die Vernetzungsknoten bilden und mindestens ein Teil der Segmente, die keine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweisen, die Verbindungen zwischen den Knoten ausbildet.
  6. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die Segmente, die keine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweisen, zumindest in diesem Temperaturbereich wasserlöslich sind.
  7. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die polymeren Segmente, die keine untere kritische Lösungstemperatur aufweisen, im Bereich der Herstellungstemperatur der Emulsion wasserlöslich sind.
  8. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem es sich bei dem polymeren Segment, das keine untere kritische Lösungstemperatur aufweist, um ein Polymer vom wasserlöslichen ethylenischen Typ handelt.
  9. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, das durch Polymerisation von wasserlöslichen ethylenischen Monomeren vom Vinyl-, Acryl-, Styrol-, Dien- und/oder Vinylester-Typ erhältlich ist.
  10. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die polymeren Segmente ein Molekulargewicht von mindestens mehr als 1000 g/mol aufweisen.
  11. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die polymeren Segmente aus der Polymerisation von Acrylsäure und/oder 2-Acrylamidomethylpropansulfonsäure stammen.
  12. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die polymeren Segmente, die eine untere kritische Lösungstemperatur zwischen 25 und 80°C aufweisen, sich von polyalkoxylierten Polymeren ableiten.
  13. Verfahren nach dem vorhergehenden Anspruch, dadurch gekennzeichnet, daß man ein thermoverdickendes Polymer verwendet, bei dem die polymeren Segmente mindestens 5 oxyalkenylierte Einheiten enthalten.
  14. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man ein unter
    aus POE-POP-POE-Triblöcken und Acrylsäure (jeweilige Molprozentanteile: 2,3%, 97,7%), vorzugsweise durch direkte Pfropfung, hergestelltem Polymer,
    aus POE-POP-POE-Triblock-Makromonomer und Acrylsäure (jeweilige Molprozentanteile: 1,6%, 98,4%), vorzugsweise durch Copolymerisation, hergestelltem Polymer,
    aus POE-POP-POE-Triblock-Makromonomer und Acrylsäure (jeweilige Molprozentanteile: 3%, 97%), vorzugsweise durch Copolymerisation, hergestelltem Polymer, und/oder
    aus POE-POP-POE-Triblock-Makromonomer und Acrylsäure (jeweilige Molprozentanteile: 2%, 98%), vorzugsweise durch Copolymerisation, hergestelltem Polymer
    ausgewähltes thermoverdickendes Polymer verwendet.
  15. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man eine derartige Menge an thermoverdickendem Polymer verwendet, daß die Viskosität der wäßrigen Phase das 0,5- bis 2fache der Viskosität der organischen Phase bei der Herstellungstemperatur der Emulsion beträgt.
  16. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man einen Gehalt an thermoverdickendem Polymer zwischen 0,5 und 5 Gew.-%, bezogen auf die wäßrige Phase, und vorzugsweise zwischen 1 und 3 Gew.-%, bezogen auf die wäßrige Phase, verwendet.
  17. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man eine organische Phase mit einer Viskosität von mindestens 5 Pa.s und vorzugsweise zwischen 5 und 500 Pa.s verwendet.
  18. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man eine unter Mineralölen, Alkydharzen, Polyisocyanaten und hochmolekularen Silikonen ausgewählte organische Phase verwendet, wobei diese Verbindungen einzeln oder als Gemisch vorliegen.
  19. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man eine organische Phase mit mindestens einem hydrophoben Wirkstoff verwendet.
  20. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man eine organische Phase mit einer dispergierten internen wäßrigen Phase verwendet.
  21. Verfahren nach Anspruch 20, dadurch gekennzeichnet, daß man eine interne wäßrige Phase mit mindestens einem hydrophilen Wirkstoff verwendet.
  22. Verfahren nach Anspruch 20 oder 21, dadurch gekennzeichnet, daß man ein Gewichtsverhältnis von interner wäßriger Phase zu organischer Phase zwischen 10/90 und 90/10 und vorzugsweise zwischen 30/70 und 80/20 verwendet.
  23. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das Gewichtsverhältnis von organischer Phase zu wäßriger Phase oder das Gewichtsverhältnis von interner wäßriger Phase und organischer Phase zusammengenommen zu wäßriger Phase zwischen 10/90 und 90/10 und vorzugsweise zwischen 30/70 und 80/20 liegt.
  24. Verfahren nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß man
    die organische Phase, enthaltend:
    gegebenenfalls mindestens einen hydrophoben Wirkstoff,
    gegebenenfalls die dispergierte interne wäßrige Phase, die gegebenenfalls einen hydrophilen Wirkstoff und gegebenenfalls mindestens ein Additiv enthält; wobei die interne wäßrige Phase und die organische Phase zusammengenommen mindestens ein nichtionisches Tensid und/oder mindestens ein amphiphiles Blockpolymer und/oder mindestens ein kationisches Tensid enthalten; und
    die wäßrige Phase, enthaltend:
    gegebenenfalls mindestens einen hydrophilen Wirkstoff,
    mindestens ein polyalkoxyliertes nichtionisches Tensid und/oder mindestens ein nichtionisches amphiphiles Polymer und/oder mindestens ein anionisches Tensid und/oder mindestens ein anionisches amphiphiles Polymer,
    mindestens ein thermoverdickendes Polymer,
    gegebenenfalls mindestens ein Additiv und gegebenenfalls mindestens ein verdickendes Polymer;
    unter Rühren vermischt.
EP01980622A 2000-10-20 2001-10-22 Verfahren zur herstellung einer emulsion, deren organische phase eine hohe viskosität hat Expired - Lifetime EP1331985B1 (de)

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FR0013465A FR2815637B1 (fr) 2000-10-20 2000-10-20 Procede de preparation d'une emulsion dont la phase huileuse est de forte viscosite
PCT/FR2001/003273 WO2002032560A2 (fr) 2000-10-20 2001-10-22 Procede de preparation d'une emulsion dont la phase organique est de forte viscosite

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FR2823450B1 (fr) * 2001-04-12 2004-08-27 Rhodia Chimie Sa Suspension obtenue a partir d'une emulsion multiple comprenant un compose hydrophobe solide a temperature ambiante et granules obtenus par sechage de la suspension
FR2848878B1 (fr) * 2002-12-23 2005-02-11 Rhodia Chimie Sa Suspension de particules presentant plusieurs phases
FR2862235B1 (fr) * 2003-11-13 2007-12-28 Rhodia Chimie Sa Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux
FR2862234B1 (fr) * 2003-11-13 2006-02-17 Rhodia Chimie Sa Emulsion pour vehiculer une matiere active hydrophobe vers un substrat en milieu aqueux
WO2006063730A1 (en) * 2004-12-15 2006-06-22 Wacker Chemie Ag Manufacture of stable silicone emulsion
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JP4723168B2 (ja) 2011-07-13
EP1331985A2 (de) 2003-08-06
DE60111412T2 (de) 2006-03-16
JP2004511630A (ja) 2004-04-15
FR2815637A1 (fr) 2002-04-26
CN1277599C (zh) 2006-10-04
ATE297248T1 (de) 2005-06-15
US20050228126A1 (en) 2005-10-13
WO2002032560A2 (fr) 2002-04-25
AU2002212424A1 (en) 2002-04-29
FR2815637B1 (fr) 2006-08-04
US20040054076A1 (en) 2004-03-18
US7288575B2 (en) 2007-10-30
DE60111412D1 (de) 2005-07-14
CN1476349A (zh) 2004-02-18
WO2002032560A3 (fr) 2002-06-27

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